CN104710583A - Preparation method for high-strength hydrogel - Google Patents
Preparation method for high-strength hydrogel Download PDFInfo
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- CN104710583A CN104710583A CN201510080672.2A CN201510080672A CN104710583A CN 104710583 A CN104710583 A CN 104710583A CN 201510080672 A CN201510080672 A CN 201510080672A CN 104710583 A CN104710583 A CN 104710583A
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Abstract
The invention discloses a preparation method for high-strength hydrogel. The method comprises the following steps: uniformly mixing chitosan, methacrylic acid, water and the like, adding montmorillonite dispersion liquid into the mixture, performing uniform stirring to form a mixed solution, removing oxygen from the mixed solution, adding an initiator into the mixed solution, and reacting at constant temperature for a certain period of time to obtain the high-strength hydrogel. According to the method, the high-strength hydrogel is polymerized and prepared by a one-step method, a micromolecular organic chemical cross-linking agent is not used in a preparation process, and the prepared hydrogel has super-high tensile property, breaking elongation capable of reaching over 3,000 percent or above and high biocompatibility, and has wide application prospects on the aspects of biosensors, artificial organs, tissue repair materials, medicine controlled release and the like in the field of biomedicine.
Description
Technical field
The invention belongs to hydrogel preparation field, be specifically related to a kind of preparation method of high intensity hydrogel.
Background technology
Macromolecule hydrogel is the three-dimensional space network structure formed after swelling in water by cross-linked polymer, and the water of 50 ~ 90% is filled in usual reticulated structure inside.As a kind of wet soft material, hydrogel is quite similar with some Organ and tissues of human body in many aspects, therefore demonstrates good application prospect at bio-medical field (in tissue renovation material, artificial muscle, biosensor and pharmaceutical carrier etc.).But traditional synthetic water gel often presents lower mechanical property, and matter is crisp frangible, hydrogel practical application request in a lot of fields can not be met.In order to improve the physical strength of hydrogel, in recent ten years, gel scholar develops some hydrogels having new network structure and improve mechanical property, relatively more typical hydrogel, organic-inorganic hybrid nanocomposite hydrogel, double-network hydrogel, four arm gels and the organic macromolecule microballoon plural gel etc. represented as having topological framework (or slip ring).
But often there is many deficiencies in the high intensity hydrogel reported, preparation as the hydrogel and four arm hydrogels with topological framework (or slip ring) needs to use the gel precursor with special construction, narrow application range high to the requirement of gel precursor.Organic-inorganic hybrid nanocomposite hydrogel, due to mainly by the network structure that physical crosslinking is formed, causes hydrogel less stable.Although the preparation of organic macromolecule microballoon composite aquogel does not need separately to add organic crosslinking agent, but need first to prepare the polymer microballoon of surface containing a large amount of free radical (or decomposable asymmetric choice net forms the group of free radical) and carry out trigger monomer polymerization as initiator and large linking agent, process is comparatively complicated.Although the double-network hydrogel be made up of the asymmetric two kinds of cross-linked networks of intensity is applicable to various of monomer, linking agent and cross-linking method, but preparation process is complicated, often need the continuous radical polymerization process of multistep, not only consuming time and need to use micromolecular organic chemistry linking agent.Therefore, develop simple high intensity hydrogel preparation method and remain a challenging job, for the practical application promoting hydrogel, there is most important theories and practical significance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high intensity hydrogel, it is prepared from by one-step polymerization reaction, and preparation technology is simple to operation, and the hydrogel prepared has superpower tensile property.
Its technical solution comprises:
A preparation method for high intensity hydrogel, comprises the following steps successively:
A, the mixture of chitosan, methacrylic acid or methacrylic acid and comonomer, water to be mixed, abundant stirring obtains homogeneous transparent solution, in described solution, solid content is 15 ~ 30%, wherein, in solid mixture, the massfraction of chitosan is 4 ~ 10%, surplus is the mixture of methacrylic acid or methacrylic acid and comonomer, and the massfraction of methacrylic acid accounts for 3 ~ 100% of methacrylic acid and comonomer total mass;
B, in gained solution, be filled with nitrogen with abundant deoxygenation, in the solution after removing oxygen, add initiator more fully to mix, the add-on of initiator is 0.5 ~ 2.5% of methacrylic acid and comonomer total mass, then be placed in the constant temperature water bath of 25 ± 1 DEG C, isothermal reaction 12-36 hour, obtains high intensity hydrogel.
Utilize methacrylic acid and chitosan reaction generating chitosan methacrylate, make water-fast chitosan originally be dissolved in water and form homogeneous solution, chitosan methacrylate salt is as the multifunctional macromolecules cross-linking agent preparing hydrogel simultaneously.
As a preferred version of the present invention, in above-mentioned steps a, in step a, after the mixture of chitosan, methacrylic acid or methacrylic acid and comonomer, water fully mix, add wherein massfraction be 0.5% montmorillonite dispersions mix, wherein, the massfraction sum of polynite and chitosan accounts for 4 ~ 10% of methacrylic acid and comonomer total mass, and the mass ratio of chitosan and polynite is 7 ~ 25:1.
Add polynite as physical crosslinking agent, prepare hydrogel with chitosan methacrylate salt composite crosslinking, be conducive to the mechanical property improving hydrogel.
As another preferred version of the present invention, in step a, above-mentioned comonomer is any one in vinylformic acid, 2-acrylamide-2-methylpro panesulfonic acid, acrylamide, NIPA, N-vinyl caprolactam, N,N-DMAA, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate.
By introducing different structure and character comonomer, a step joint comonomer consumption of going forward side by side, regulates the mechanical property of hydrogel, swelling behavior and stimuli responsive performance, thus obtains multiple difference in functionality hydrogel.
Further, above-mentioned initiator is any one in Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
The preparation method of above-mentioned montmorillonite dispersions is: polynite be added to the water, mechanical stirring 30 minutes, and ultrasonic disperse obtains for 2 hours.
The solid content of above-mentioned solution is 18 ~ 25%.
The add-on of above-mentioned initiator is 0.8 ~ 1.5% of methacrylic acid and comonomer total mass.
The Advantageous Effects that the present invention brings:
The present invention proposes a kind of preparation method of high intensity hydrogel, first the mixture of chitosan, methacrylic acid or methacrylic acid and comonomer, water mix by it, form mixing solutions, then add initiator by after this mixing solutions deoxygenation, isothermal reaction prepares high intensity hydrogel after for some time; As of the present invention one preferably, it adds montmorillonite dispersions in the mixed solution of chitosan, methacrylic acid or methacrylic acid and comonomer, water; It is in the selection of raw material, by adding montmorillonite dispersions, as physical crosslinking agent, being conducive to gel mechanical property and improving;
The present invention is reacted by one-step polymerization and prepares high intensity hydrogel, does not use micromolecular organic chemistry linking agent in preparation process; Obtained hydrogel has superpower tensile property (elongation at break is up to more than 3000%), good biocompatibility and pH-, temperature response (part has) performance, and in bio-medical field, (in the controlled release etc. of biosensor, artificial organ, tissue renovation material, medicine) has wide practical use.
Prepared by the present invention is single network aqueous gel, small molecules organic crosslinking agent is not used in its preparation, relative to the preparation method of prior art hydrogel disclosed in CN103739861A, what it was prepared is double-network hydrogel, agar used, gelatin etc. form the first heavy network wherein, and the monomers such as acrylamide form the second heavy network; Often heavy network all needs cross-linking agents, as the linking agent of the polyvalent metal ion that wherein adds mainly the first heavy network; The linking agent of the second heavy network is N, N ' the dual functional organic molecule linking agent such as-methylene-bisacrylamide; Preparation technology of the present invention is simple, and its tensile strength of the hydrogel prepared is 2.0MPa ~ 3.7MPa, tensile modulus is 180KPa ~ 370KPa, tension fracture elongation rate is 1500% ~ 3800%, and modulus of compression is 95KPa ~ 305KPa, and compressive strain is all greater than 98%.
Embodiment
The present invention proposes a kind of preparation method of high intensity hydrogel, in order to make advantage of the present invention, technical scheme clearly, clearly, below in conjunction with specific embodiment, explanation clear, complete further being done to the present invention.
The invention provides a kind of preparation method of high intensity hydrogel, it is in the selection of raw material, that selects has polynite, chitosan, methacrylic acid, comonomer (vinylformic acid, 2-acrylamide-2-methylpro panesulfonic acid, acrylamide, NIPA, N-vinyl caprolactam, N, N-DMAA, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate), initiator (Potassium Persulphate, ammonium persulphate or Sodium Persulfate), above-mentioned raw materials is all bought by commercial channel and is obtained.
A preparation method for high intensity hydrogel, it specifically comprises the following steps:
Step 1, chitosan, methacrylic acid to be mixed with water three, or the mixture of chitosan, methacrylic acid and comonomer and water are mixed, fully stir and obtain homogeneous transparent solution; In this solution, solid content is 15 ~ 30%, wherein, in solid mixture, the massfraction of chitosan is 4 ~ 10%, and surplus is the mixture of methacrylic acid or methacrylic acid and comonomer, and the massfraction of methacrylic acid accounts for 3 ~ 100% of methacrylic acid and comonomer total mass;
Step 2, in gained mixing solutions, be filled with nitrogen with abundant deoxygenation, in the mixing solutions after removing oxygen, add initiator more fully to mix, the add-on of initiator is 0.5 ~ 2.5% of methacrylic acid and comonomer total mass, then be placed in the constant temperature water bath of 25 ± 1 DEG C, isothermal reaction 12-36 hour, obtains high intensity hydrogel.
It is following that the present invention will be further described in conjunction with specific embodiments:
Embodiment 1:
Chitosan, methacrylic acid are mixed with water three, fully stirs and obtain mixing solutions; In this mixing solutions, solid content is 15%, and wherein, in solid mixture, the massfraction of chitosan is 10%.
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate is 1.5% of methacrylic acid total mass, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 0.4MPa, tensile modulus is 50KPa, tension fracture elongation rate is 1300%, and modulus of compression is about 25KPa, compressive strain is greater than 98%.
Embodiment 2:
Difference from Example 1 is: in mixing solutions, solid content is 30%, and wherein in solid mixture, the massfraction of chitosan is 4%.
The hydrogel that the present embodiment prepares, tensile strength is 1.6MPa, tensile modulus is 180KPa, tension fracture elongation rate is 1900%, and modulus of compression is about 110KPa, compressive strain is greater than 98%.
Embodiment 3:
Difference from Example 1 is: in mixing solutions, solid content is 18%, and in solid mixture, the massfraction of chitosan is 5.5%.
The hydrogel that the present embodiment prepares, tensile strength is 1.8MPa, tensile modulus is 195KPa, tension fracture elongation rate is 3000%, and modulus of compression is about 95KPa, compressive strain is greater than 98%.
Embodiment 4:
Difference from Example 1 is: in mixing solutions, solid content is 18%, and in solid mixture, the massfraction of chitosan is 7%.
The hydrogel that the present embodiment prepares, tensile strength is 2.6MPa, tensile modulus is 250KPa, tension fracture elongation rate is 3000%, and modulus of compression is about 195KPa, compressive strain is greater than 98%.
Embodiment 5:
Difference from Example 1 is: in mixing solutions, solid content is 18%, and in solid mixture, the massfraction of chitosan is 10%.
The hydrogel that the present embodiment prepares, tensile strength is 2.2MPa, tensile modulus is 235KPa, tension fracture elongation rate is 3200%, and modulus of compression is about 215KPa, compressive strain is greater than 98%.
Embodiment 6:
Chitosan, methacrylic acid, acrylamide are mixed with water, fully stirs and obtain mixing solutions; In this mixing solutions, solid content is 18%, and wherein, in solid mixture, the massfraction of chitosan is 7%, and the massfraction of methacrylic acid accounts for 50% of methacrylic acid and acrylamide total mass;
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate be methacrylic acid and acrylamide quality and 1.5%, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 2.0MPa, tensile modulus is 220KPa, tension fracture elongation rate is 3400%, and modulus of compression is about 300KPa, compressive strain is greater than 98%.
Embodiment 7:
Chitosan, methacrylic acid, vinylformic acid are mixed with water, fully stirs and obtain mixing solutions; In this mixing solutions, solid content is 18%, and wherein, in solid mixture, the massfraction of chitosan is 7%, and the massfraction of methacrylic acid accounts for 50% of methacrylic acid and vinylformic acid total mass
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate be methacrylic acid and vinylformic acid quality and 1.5%, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 1.5MPa, tensile modulus is 180KPa, tension fracture elongation rate is 2100%, and modulus of compression is about 205KPa, compressive strain is greater than 98%.
Embodiment 8:
A certain amount of polynite is added to the water abundant stirring 30 minutes, ultrasonic disperse after 2 hours, obtained polynite massfraction is the montmorillonite dispersions of 0.5%;
Chitosan, methacrylic acid are mixed with water three, fully stirs and obtain mixing solutions, add montmorillonite dispersions wherein; In this mixing solutions, solid content is 18%, and wherein, the massfraction of chitosan and polynite in solid mixture is 5%, and the mass ratio of chitosan and polynite is 15.
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate is 1.5% of methacrylic acid total mass, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 2.7MPa, tensile modulus is 300KPa, tension fracture elongation rate is 3600%, and modulus of compression is about 260KPa, compressive strain is greater than 98%.
Embodiment 9:
A certain amount of polynite is added to the water abundant stirring 30 minutes, ultrasonic disperse after 2 hours, obtained polynite massfraction is the montmorillonite dispersions of 0.5%;
Chitosan, methacrylic acid are mixed with water three, fully stirs and obtain mixing solutions, add montmorillonite dispersions wherein; In this mixing solutions, solid content is 18%, and wherein, the massfraction of chitosan and polynite in solid mixture is 8%, and the mass ratio of chitosan and polynite is 15.
In above-mentioned mixing solutions, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, persulfate aqueous solution is added again in mixing solutions, the add-on of Potassium Persulphate is 1.5% of methacrylic acid total mass, then solution is transferred in reaction mould and react 12 hours under 25 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that the present embodiment prepares, tensile strength is 3.7MPa, tensile modulus is 370KPa, tension fracture elongation rate is 3800%, and modulus of compression is about 305KPa, compressive strain is greater than 98%.
Comparative example 1:
By 0.15g N, N '-methylene-bisacrylamide, 2.1g methacrylic acid, 11.75g water add in Erlenmeyer flask respectively, stirring and dissolving, in solution, inflated with nitrogen is to remove oxygen, after abundant deoxygenation, then add persulfate aqueous solution in solution, it is obtained that persulfate aqueous solution is that 0.0338g Potassium Persulphate is dissolved in 1mL water, then solution is transferred in reaction mould and react 24 hours under 25 ± 1 DEG C of constant temperatures, obtain hydrogel.
The hydrogel that this comparative example prepares, tensile strength is 0.07MPa, tensile modulus is 3KPa, tension fracture elongation rate is 25%, compressive strength 65KPa, compressive strain 75%.
All the other comonomers do not exemplified are as the vinyl monomer such as polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, and the combination that those skilled in the art obtain under enlightenment of the present invention, all should within protection scope of the present invention.
Claims (8)
1. a preparation method for high intensity hydrogel, is characterized in that, comprises the following steps:
A, the mixture of chitosan, methacrylic acid or methacrylic acid and comonomer, water to be mixed, abundant stirring obtains homogeneous transparent solution, in described solution, solid content is 15 ~ 30%, wherein, in solid mixture, the massfraction of chitosan is 4 ~ 10%, surplus is the mixture of methacrylic acid or methacrylic acid and comonomer, and the massfraction of methacrylic acid accounts for 3 ~ 100% of methacrylic acid and comonomer total mass;
B, in gained solution, be filled with nitrogen with abundant deoxygenation, in the solution after removing oxygen, add initiator more fully to mix, the add-on of initiator is 0.5 ~ 2.5% of methacrylic acid and comonomer total mass, then be placed in the constant temperature water bath of 25 ± 1 DEG C, isothermal reaction 12-36 hour, obtains high intensity hydrogel.
2. the preparation method of high intensity hydrogel according to claim 1, it is characterized in that: in step a, after the mixture of chitosan, methacrylic acid or methacrylic acid and comonomer, water fully mix, add wherein massfraction be 0.5% montmorillonite dispersions mix, wherein, the massfraction sum of polynite and chitosan accounts for 4 ~ 10% of methacrylic acid and comonomer total mass, and the mass ratio of chitosan and polynite is 7 ~ 25:1.
3. the preparation method of high intensity hydrogel according to claim 1 and 2, it is characterized in that: in step a, described comonomer is any one in vinylformic acid, 2-acrylamide-2-methylpro panesulfonic acid, acrylamide, NIPA, N-vinyl caprolactam, N,N-DMAA, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate.
4. the preparation method of high intensity hydrogel according to claim 3, is characterized in that: in step b, and described initiator is any one in Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
5. the preparation method of high intensity hydrogel according to claim 3, is characterized in that: the preparation method of montmorillonite dispersions is: polynite be added to the water, mechanical stirring 30 minutes, and ultrasonic disperse obtains for 2 hours.
6. the preparation method of high intensity hydrogel according to claim 3, is characterized in that: the solid content of described solution is 18 ~ 25%.
7. the preparation method of high intensity hydrogel according to claim 3, is characterized in that: in step b, and the add-on of initiator is 0.8 ~ 1.5% of methacrylic acid and comonomer total mass.
8. the preparation method of high intensity hydrogel according to claim 2, is characterized in that: the massfraction sum of polynite and chitosan accounts for 6 ~ 8% of methacrylic acid and comonomer total mass, and the mass ratio of chitosan and polynite is 10 ~ 15:1.
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Cited By (3)
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| CN107537446A (en) * | 2017-10-10 | 2018-01-05 | 长沙爱扬医药科技有限公司 | Organic montmorillonite carried titanium dioxide material and preparation method thereof |
| CN113150320A (en) * | 2021-03-31 | 2021-07-23 | 中国地质大学（武汉） | Preparation method and application of irradiation-initiated chitosan-based double-network high-strength hydrogel |
| CN113461971A (en) * | 2021-06-28 | 2021-10-01 | 广州大学 | Conductive hydrogel and preparation method and application thereof |
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| CN113150320A (en) * | 2021-03-31 | 2021-07-23 | 中国地质大学（武汉） | Preparation method and application of irradiation-initiated chitosan-based double-network high-strength hydrogel |
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| CN113461971B (en) * | 2021-06-28 | 2023-12-26 | 广州大学 | Conductive hydrogel and preparation method and application thereof |
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